CN106345319B - It is a kind of without support full carbon film of active carbon and its preparation method and application - Google Patents
It is a kind of without support full carbon film of active carbon and its preparation method and application Download PDFInfo
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- CN106345319B CN106345319B CN201610734288.4A CN201610734288A CN106345319B CN 106345319 B CN106345319 B CN 106345319B CN 201610734288 A CN201610734288 A CN 201610734288A CN 106345319 B CN106345319 B CN 106345319B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 183
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 13
- 230000001105 regulatory effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 208000006735 Periostitis Diseases 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 210000003460 periosteum Anatomy 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
- B01D71/0211—Graphene or derivates thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
- B01D67/00416—Inorganic membrane manufacture by agglomeration of particles in the dry state by deposition by filtration through a support or base layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0044—Inorganic membrane manufacture by chemical reaction
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- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0046—Inorganic membrane manufacture by slurry techniques, e.g. die or slip-casting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/308—Pore size
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2323/30—Cross-linking
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Abstract
The invention discloses a kind of without support full carbon film of active carbon and its preparation method and application.The full carbon film of active carbon formed is connected as crosslinking agent by graphene, which can be stabilized independently of substrate, while have very high chemically-resistant corrosion resistance and thermal stability.This multi-functional full carbon film has controllable pore structure, and simultaneously for pollutant absorption property with super strength, pore size can be realized to regulate and control from micron order to nanoscale under the regulation of crosslinking agent additive amount and be adjusted.According to above-mentioned property, which can realize the effect of step removal particulate pollutant and small molecule contaminants, can be used for the processing of environmental pollution water body, the fields such as drink water purifying and air cleaning.
Description
Technical field
The invention belongs to field of material preparation more particularly to a kind of without support full carbon film of active carbon and preparation method thereof and answer
With.
Background technique
Active carbon is the adsorbent material being most widely used, extensive due to its huge specific surface and abundant pore structure
Applied to water body, gas purification, chemical catalysis, the fields such as energy storage.Application referring now to active carbon is often with particulate form
Form is added directly in polluted-water and is adsorbed, but this application often will cause the loss of active carbon, be related to simultaneously
The time-consuming and laborious separation of solid and liquid process in later period.Also having application is active carbon to be filled in container, or be embedded in poly
Carried out in object using.But active carbon packed column is easy contaminated blocking in use, and inlaying for polymer can block
Activated carbon pore structure and masking surface texture, influence its absorption property.Meanwhile the fixed active carbon of container or physics of filling
Polymer tend not to keep out the erosion and high-temperature operation of chemical substance, limit its application field, so, study and develop
Novel active carbon device has a very important significance the application of active carbon.
Summary of the invention
It is an object of the invention to solve problems of the prior art, and provide a kind of without the support full carbon film of active carbon
And its preparation method and application, while not only having ensure that its superpower absorption property, but also the ability for making it have particulate matter retention,
Extensive space is provided for the application of active carbon.
Since active carbon has huge specific surface area and pore structure abundant, have for dissolved pollutant in water
There is superpower absorption property, active carbon has very big application potential in different fields.But since active carbon particle is larger
The limitation of size and irregular surface, is difficult between active carbon particle to interact and further device.In order to solve list
Weak, the problem of device hardly possible of pure active carbon particle interaction, while high molecular polymer is not introduced, present invention employs one kind
Completely new thinking: it using the pi-electron structure of activated carbon surface, is crosslinked with the graphene with armaticity surface as carbonaceous
Agent makes particulate form active carbon form a film by the π-π interaction force of active carbon and carbonaceous crosslinking agent surface, is guaranteeing its adsorption energy
The ability of its particle entrapment is assigned while power.This multi-functional full carbon film has controllable pore structure, simultaneously for pollution
Object absorption property with super strength, pore size can be realized under the regulation of crosslinking agent additive amount to be regulated and controled from micron order to receiving
The adjusting of meter level.
The purpose of the present invention is realized particular by following technical scheme:
It is basic material by active carbon without the support full carbon film of active carbon, graphene connects to form active carbon as crosslinking agent
Full carbon film.π-π the interaction force of active carbon and carbonaceous crosslinking agent surface makes the formation of particulate form active carbon not need support construction
Full carbon film.
Another object of the present invention is to provide a kind of preparation methods without the support full carbon film of active carbon, including following step
It is rapid: active carbon being dispersed in water first, active carbon dispersion liquid is formed, adds graphene dispersing solution, and mix well, will mix
Solution after even is filtered, and assembles graphene and active carbon in filter membrane substrate, obtains the full carbon film of active carbon.Activity
The full carbon film of charcoal can be removed after drying from substrate surface, form independent full carbon film.
Preferably, the size of the active carbon is micron order, it is therefore an objective to make it easier to disperse in water.
Preferably, adjusting pH in alkalinity in active carbon dispersion process.PH preferably controls > 10, has active carbon in water
There is stronger electrostatic repulsion (> -30mV), further enhances its dispersibility.
Preferably, the graphene dispersing solution is obtained by graphene oxide dispersion partial reduction.Utilize crosslinking agent
Non-covalent bond π between active carbon makes granular activated carbon device be innovative point of the invention with friendship active force, is guaranteeing carbon
Under the premise of matter crosslinking agent is fully dispersed in water, restore as far as possible the oxygen-containing extension in its surface can roll into a ball can be enhanced its hydrophobic effect and
Surface pi-electron system is conducive to the stability of film forming.
Further, reduction process realizes that partial reduction process is, by the stone in graphene aqueous solution by electronation
Black alkene control is controlled in 0.05-0.1mg/ml, pH in 9-12, then carries out heating reduction again.PH value of solution is controlled in 9-12, is protected
Stronger electrostatic repulsion between carbonaceous crosslinking agent is demonstrate,proved, keeps it fully dispersed in water, prevents its reunion, pH is preferably 11.Simultaneously
Reunion caused by concentration control prevents concentration higher in 0.05-0.1mg/ml
Preferably, the solution after mixing is placed in pressure filter, filtered by the method for pressure filtration by micropore
Film substrate film forming.Driving force can be nitrogen in pressure filter, be also possible to other gases, pressure control range is
0.05-0.6Mpa, it is therefore an objective to allow mixed liquor filtering assembling process between shorter within complete (< 30min), prevent the time
Too long active carbon dispersion liquid precipitates, and leads to the uneven of film forming.It pressure filter bottom need to be using miillpore filter as base
Bottom carries out lamination assembling, filters the miillpore filter substrate of assembling there is no material requirement, function is that retention active carbon and carbonaceous are handed over
Connection agent is assembled, but surface is smooth small with activated carbon effect power can be conducive to remove after film forming from substrate surface.
Preferably, the ratio of graphene is adjustable, and the mass ratio of graphene and active carbon is preferred in solution after mixing
It is 1%~10%.The thickness of activated charcoal membrane can be regulated and controled by the additive amount of active carbon, and the surface pore structure of activated charcoal membrane can
Regulated and controled with the ratio added by carbonaceous crosslinking agent.
The present invention provides a kind of modes of novel absorbent charcoal device, and active carbon is made not add high molecular polymer item
It independently forms a film under part, membrane body has superpower pore structure and specific surface area.Implement the film in use to have the advantage that and high score
Sub- polymeric membrane is compared, the full carbon film of active carbon chemical stability with super strength and thermal stability.With pure graphene film or carbon nanometer
The full carbon film of periosteum is compared, and active carbon has preferable price advantage since preparation cost is cheap.Meanwhile passing through carbonaceous crosslinking agent
Additive amount control can the efficient regulation that must realize membrane pores size, it is selective to retain various sizes of particle contamination
Object.The study found that the full carbon film of active carbon can be with the microorganism in effectively catching water body, nano particle, and it can efficiently remove depollution
Dyes, polycyclic aromatic hydrocarbon, the dissolved pollutants such as heavy metal ion.
It, can be in water body since the full carbon film of active carbon is provided simultaneously with superpower absorption property and controllable pore structure
There is very big application potential in the fields such as purification, air cleaning, chemical catalysis or energy reserves.
Detailed description of the invention
Fig. 1 is the electron-microscope scanning figure of full carbon film made from embodiment 1；
Fig. 2 is the electron-microscope scanning figure of full carbon film made from embodiment 3；
Fig. 3 is the electron-microscope scanning figure of full carbon film made from embodiment 5；
Fig. 4 is the electron-microscope scanning figure of full carbon film made from embodiment 7.
Specific embodiment
The present invention is further elaborated with reference to the accompanying drawings and examples, so that those skilled in the art more fully understand
Essence of the invention.Reagent or material in the present invention, if being commercial product without specified otherwise.
Graphene dispersing solution preparation:
Graphene dispersing solution is prepared by graphene oxide dispersion partial reduction.Specifically: graphene oxide is configured to
Aqueous solution, graphene control makes graphene exist in 9-12 in 0.05-0.1mg/ml, pH control to realize that electrostatic regulates and controls in solution
It can be fully dispersed in water.Above-mentioned solution carries out heating reduction 15 minutes at 90 DEG C, obtains graphene oxide dispersion.
Above-described embodiment is preferred embodiment of the invention, and each parameter can be adjusted according to actual needs, simultaneously
Graphene dispersing solution directly can also be dispersed to obtain by graphene particles under Action of Surfactant.Or it can also be with
Using other graphene dispersing solutions in the prior art.
Embodiment
Film forming procedure of the invention realizes that active carbon and graphene are regulated and controled by electrostatic first before filtering by filtering assembling
Keep it fully dispersed in water.Active carbon and graphene dispersing solution are sufficiently mixed with certain proportion, are then added in filter device,
So that it is crossed miillpore filter under the action of driving force, and is assembled in miillpore filter substrate surface.Preparation is without support active carbon
Specific step is as follows for full carbon film:
(1) active carbon passes through first grinds and passes through 500 mesh screens, guarantees it having a size of micron order.
(2) micron-sized active carbon is added to the water, adjusts solution ph to 11, is regulated and controled using surface electrostatic, in ultrasound
Under the action of granular activated carbon is well-dispersed in water, obtain active carbon dispersion liquid.It should be noted that in the step, pH
Electrostatic regulating effect can be influenced, when pH controls>10, activated carbon surface electronegativity<-30mV, ultrasonication time are 2min at this time,
Guarantee that active carbon particle in water can be fully dispersed.But as long as pH keeps alkalinity, dispersion effect also can be realized substantially.
It (3) will be sufficiently mixed under conditions of the aforementioned graphene dispersing solution prepared and the earthquake of active carbon dispersion liquid and ultrasound
It closes, the mass ratio of graphene and active carbon is successively adjusted to 1%, 2%, 3%, 4%, 5%, 6%, 7% in mixed liquor, remembers respectively
For 1~embodiment of embodiment 7.
(4) active carbon well-mixed in each embodiment+carbonaceous crosslinking agent mixed liquor is successively placed in pressure filter
In, using nitrogen as pressurization gas, pressure limit 0.05-0.6Mpa, miillpore filter substrate aperture is 0.22 substrate, and mixed liquor exists
Fast filming in 30min.
(5) it after dry, removes full carbon film to form independent full carbon film from miillpore filter substrate.
Full carbon film resulting to embodiment 1,3,5,7 carries out electron-microscope scanning, and result is as described in Figure 1.In figure, it can see
Out, it under the crosslinked action of graphene, is connected with each other, is formed whole as between the active carbon particle of basic material.While with
The increase of graphene amount, surface texture gradually become fine and close, pore structure becomes smaller.Meanwhile the thickness of activated charcoal membrane can be with
Regulated and controled by the volume that active carbon dispersion liquid adds, addition is more, and film layer is thicker, and the adsorption capacity of film is bigger.
Using the resulting full carbon film of Examples 1 to 7 respectively to chlorella, Escherichia coli, nano silica, nano silver into
Row filtering rejection tests.Test result is as shown in table 1, and the activated charcoal membrane of different graphene additive amount ratios has different holes
Structure speciality.It, can be with 100% trapped particles having a size of 2 μm when graphene additive amount reaches the 1% of the quality of active carbon
Chlorella.It, can be with 100% trapped particles having a size of 1 μm when graphene adding proportion reaches the 2% of the quality of active carbon
Escherichia coli.It, can be with 100% trapped particles having a size of 200nm when graphene adding proportion reaches the 3% of the quality of active carbon
Nano silica.When graphene adding proportion reaches the 7% of the quality of active carbon, fenestra gap structure be can achieve
24nm, can nano silver with 99.23% trapped particles having a size of 50nm.It can be seen that the pore structure of film can pass through carbonaceous
Crosslinking agent adding proportion is adjusted, and crosslinking agent adding proportion is higher, and the pore structure of film is smaller.Full carbon film of the invention can be with
Microorganism, nano particle in effectively catching water body.In addition its can be used for removal polluted-water in dyestuff, polycyclic aromatic hydrocarbon,
The dissolved pollutants such as heavy metal ion.
Interception capacity of the full carbon film of the different graphene contents of table 1. for particulate matter
Above-mentioned embodiment is only a preferred solution of the present invention, so it is not intended to limiting the invention.Example
Such as, although in above-described embodiment, active carbon is obtained after grinding by 500 mesh screens, is not meant to that it must be through
500 mesh screens are crossed, as long as being able to maintain active carbon particle in the micron-scale or even nanoscale, can realize effect of the invention.
For another example the case where above-described embodiment only lists, and the mass ratio of graphene and active carbon is 1%~7% in mixed liquor, but pass through
Overtesting is adjusted before and after the range, such as mass ratio is 9%, 10% or even 10% or more, also can be realized this hair
Bright technical effect, but the properties such as water flux can slightly decline.
It can be seen that those skilled in the art may be used also without departing from the spirit and scope of the present invention
To make a variety of changes and modification.Therefore all mode technical solutions obtained for taking equivalent substitution or equivalent transformation, fall
Within the scope of the present invention.
Claims (7)
1. a kind of preparation method without the support full carbon film of active carbon characterized by comprising
Active carbon is dispersed in water, active carbon dispersion liquid is formed, adds graphene dispersing solution, and mix well, will mix
Solution afterwards is filtered, and assembles graphene and active carbon in filter membrane substrate, obtains the full carbon film of active carbon；It is described
Active carbon size be micron order；In active carbon dispersion process, pH is adjusted in alkalinity；The graphene dispersing solution is by aoxidizing
Graphene aqueous dispersions partial reduction obtains.
2. the preparation method as described in claim 1 without the support full carbon film of active carbon, which is characterized in that control pH > 10.
3. the preparation method as described in claim 1 without the support full carbon film of active carbon, which is characterized in that partial reduction process
In, graphene concentration control in graphene aqueous solution is controlled in 9-12, restored in 0.05-0.1 mg/ml, pH.
4. the preparation method as described in claim 1 without the support full carbon film of active carbon, which is characterized in that the solution after mixing
It is placed in pressure filter, is formed a film by the method for pressure filtration by miillpore filter substrate.
5. the preparation method as claimed in claim 4 without the support full carbon film of active carbon, which is characterized in that filtration time < 30
min。
6. the preparation method as described in claim 1 without the support full carbon film of active carbon, which is characterized in that the hole of full carbon film
It can be adjusted by the additive amount of graphene.
7. a kind of method as described in claim 1 preparation without the support full carbon film of active carbon, which is characterized in that be by active carbon
Basic material, graphene connect to form the full carbon film of active carbon as crosslinking agent.
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| CN201610734288.4A CN106345319B (en) | 2016-08-25 | 2016-08-25 | It is a kind of without support full carbon film of active carbon and its preparation method and application |
| CN201780003007.0A CN108136340A (en) | 2016-08-25 | 2017-08-25 | A kind of full carbon film based on activated carbon and its preparation method and application |
| PCT/CN2017/098964 WO2018036553A1 (en) | 2016-08-25 | 2017-08-25 | All-carbon film based on activated carbon and preparation method and use thereof |
| US16/328,205 US20190176096A1 (en) | 2016-08-25 | 2017-08-25 | All-Carbon Film Based On Activated Carbon And Preparation Method And Use Thereof |
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| CN106345319B (en) * | 2016-08-25 | 2019-05-17 | 浙江大学 | It is a kind of without support full carbon film of active carbon and its preparation method and application |
| CN109985534B (en) * | 2017-12-30 | 2021-08-10 | 浙江大学 | Pure active carbon filtering membrane and preparation method and application thereof |
| CN108579452A (en) * | 2018-06-15 | 2018-09-28 | 南京水杯子科技股份有限公司 | A kind of compound carbon membrane of graphene oxide and preparation method thereof |
| CN109126284B (en) * | 2018-09-30 | 2019-10-25 | 江南大学 | A kind of preparation method of graphene modified polypropene composite filtering material |
| CN110372109A (en) * | 2019-06-25 | 2019-10-25 | 南通强生石墨烯科技有限公司 | A kind of graphene scale inhibition filter core and preparation method thereof |
| CN110860215B (en) * | 2019-10-12 | 2020-12-08 | 浙江大学 | Graphene oxide film with tent-like structure and preparation method and application thereof |
| CN112642308A (en) * | 2019-12-03 | 2021-04-13 | 贵州省材料技术创新基地 | Polysulfone-biochar blending separation membrane and preparation method thereof |
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| CN108136340A (en) | 2018-06-08 |
| CN106345319A (en) | 2017-01-25 |
| US20190176096A1 (en) | 2019-06-13 |
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